WO2015046842A1 - Procédé de préparation d'épargne de soudage et film sec, et stratifié pelliculaire utilisé dans ce procédé - Google Patents

Procédé de préparation d'épargne de soudage et film sec, et stratifié pelliculaire utilisé dans ce procédé Download PDF

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Publication number
WO2015046842A1
WO2015046842A1 PCT/KR2014/008791 KR2014008791W WO2015046842A1 WO 2015046842 A1 WO2015046842 A1 WO 2015046842A1 KR 2014008791 W KR2014008791 W KR 2014008791W WO 2015046842 A1 WO2015046842 A1 WO 2015046842A1
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WIPO (PCT)
Prior art keywords
film
resin composition
solder resist
transparent carrier
group
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PCT/KR2014/008791
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English (en)
Korean (ko)
Inventor
정민수
경유진
최병주
정우재
최보윤
이광주
구세진
Original Assignee
주식회사 엘지화학
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Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US14/763,414 priority Critical patent/US9788434B2/en
Priority to CN201480013033.8A priority patent/CN105190442B/zh
Priority to JP2015546407A priority patent/JP6047666B2/ja
Publication of WO2015046842A1 publication Critical patent/WO2015046842A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/325—Non-aqueous compositions
    • G03F7/327—Non-aqueous alkaline compositions, e.g. anhydrous quaternary ammonium salts
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
    • H01L21/4814—Conductive parts
    • H01L21/4846—Leads on or in insulating or insulated substrates, e.g. metallisation
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/027—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed by irradiation, e.g. by photons, alpha or beta particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/281—Applying non-metallic protective coatings by means of a preformed insulating foil
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3452—Solder masks

Definitions

  • the present invention relates to a method for producing DFSR that enables the formation of a dry film solder resist (DFSR) having fine irregularities on its surface in a simpler manner, and to a film laminate used therein.
  • DFSR dry film solder resist
  • photosensitive and solder resists capable of forming minute openings and patterns are used in printed circuit boards, semiconductor package substrates, and flexible circuit boards.
  • solder resists characteristics such as developability, high resolution, insulation, soldering heat resistance, and gold plating resistance are generally required.
  • film type as needed Fine surface irregularities are formed on the solder resist.
  • a separate surface treatment process such as a plasma treatment process may be performed,
  • the method of changing the composition itself for forming DFSR, and the like were applied.
  • a separate treatment process such as the plasma treatment process is added or a change of composition is involved, there is a disadvantage in that the complexity and economical efficiency of the overall process are greatly caused.
  • the present invention provides a method for producing DFSR that enables the formation of DFSR having fine unevenness on the surface in a simpler manner without additional process addition or composition change.
  • This invention also provides the film laminated body used as an intermediate body etc. in the manufacturing method of said DFSR.
  • the present invention relates to (a) a carboxyl group (-CO is H), an acid-modified oligomer having a photocurable unsaturated functional group, (b) a photopolymerizable monomer having two or more photocurable unsaturated functional groups, and (c) a thermosetting Forming a resin composition having a thermosetting binder having a possible functional group and (d) a photocurable and thermosetting comprising a photoinitiator on a transparent carrier film with a fine roughness of average roughness (Ra 50nm to 5 / / m formed on the surface .
  • the present invention also provides a surface-carrier average roughness (transparent carrier film having a fine concavo-convex having a Rap of 50 nm to 5 kPa);
  • a resin composition having a photocurable and thermosetting composition comprising a polymer, (b) a photopolymerizable monomer having two or more photocurable unsaturated functional groups, (c) a thermosetting binder having a thermosetting functional group, and (d) a photoinitiator.
  • the resin composition layer provides a film laminate for forming DFSR having a gelation time of 2 to 5 minutes under the conditions of 0.4 g and 16 CTC.
  • the film laminated body for DFSR used for this is demonstrated in detail.
  • thermosetting binder a carboxyl group (-COOH), an acid-modified oligomer having a photocurable unsaturated functional group, (b) a photopolymerizable monomer having two or more photocurable unsaturated functional groups, (c) having thermosetting functional groups Forming a thermosetting binder and (d) a photocurable and thermosetting resin composition comprising a photoinitiator on a transparent carrier film having fine irregularities having an average roughness (Ra) of 50 nm or more on a surface thereof; Stacking the resin composition on a substrate to form a laminated structure in which a substrate, a resin composition, and a transparent carrier film are sequentially formed; Exposing to the resin composition, and peeling off the transparent carrier film; And alkali developing and thermally curing the resin composition of the non-exposed part is provided.
  • a manufacturing method after forming a general photocurable and thermosetting resin composition for forming DFSR on a transparent carrier film having a surface fine unevenness, and then proceeds to the subsequent DFSR manufacturing process, fine unevenness on the transparent carrier film is applied to the DFSR.
  • the DFSR reflecting and finally having fine irregularities can be produced well. That is, in the manufacturing method of the embodiment, the surface having fine irregularities in a simpler manner using only the transparent carrier film having the surface fine irregularities formed without the addition of a separate process such as a plasma treatment process or a change in the composition for forming DFSR. DFSR can be formed.
  • a resin composition having photocurability and thermosetting property is basically used.
  • a resin composition contains a carboxy group (-COOH) and an acid-modified oligomer which has a photocurable unsaturated functional group as one of the main components.
  • acid-modified oligomers may be combined with other components of the resin composition by photocuring, namely photopolymerizable monomers and / or thermosetting binders.
  • Crosslinking is formed to enable the formation of DFSR, and the resin composition, including carboxyl groups, exhibits alkali developability.
  • Such acid-modified oligomers include all components known to be usable in photocurable resin compositions from before the oligomers having a carboxyl group and a photocurable functional group, for example, an acrylate group or a curable functional group having an unsaturated double bond in the molecule.
  • the main chain of such acid-modified ligomer may be a novolak sepoxy or polyurethane, and may be used as an acid-modified oligomer having a carboxyl group and an acrylate group introduced therein.
  • the photocurable functional group may suitably be an acrylate group, wherein the acid-modified oligomer is a copolymer of oligomer form in which a polymerizable monomer having a carboxyl group and a monomer including an acrylate compound and the like are co-condensed. It may include.
  • acid-modified oligomer usable for the resin composition include the following components.
  • ethylenically unsaturated groups such as vinyl groups, allyl groups, (meth) acryloyl groups, epoxy groups, acid chlorides, and the like, as part of the co-polymer of the unsaturated carboxylic acid (a) and the compound (b) having an unsaturated double bond
  • a carboxyl group-containing photosensitive resin obtained by reacting a compound having a semi-aromatic group, for example, glycidyl (meth) acrylate and adding an ethylenically unsaturated group as a pendant;
  • (6) 1 molecule increase such as a C2-C17 alkylcarboxylic acid aromatic group containing alkylcarboxylic acid, of the epoxy group of the copolymer of the compound (b) and glycidyl (meth) acrylate which have an unsaturated double bond
  • a carboxyl group-containing resin obtained by reacting an organic acid (j) having two carboxyl groups and not having an ethylenically unsaturated bond and reacting a saturated or unsaturated polybasic acid anhydride (d) with the resulting secondary hydroxy group;
  • diisocyanates (j) such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates; and carboxyl group-containing dialcohol compounds (k) such as dimethylolpropionic acid and dimethylolbutanoic acid, and polycarboxes;
  • Diol compounds such as compounds having carbonate polyols, polyether polys, polyester polys, polyolefin polys, acrylic polys, bisphenol A alkylene oxide adducts, phenolic hydroxyl groups and alcoholic hydroxyl groups ( carboxyl group-containing urethane resin in which the middle part of m) is obtained by reaction;
  • diisocyanate (j) bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, non (Meth) acrylate of bifunctional epoxy resins, such as a phenol type epoxy resin, or Photosensitive carboxyl group-containing urethane resin obtained by the polyaddition reaction of its partial acid anhydride modified substance (n), a carboxyl group-containing dialcoul compound (k), and a diol compound (m);
  • Carboxyl group-containing urethane resin which added the compound which has a (meth) acryloyl group, and was terminal (meth) acrylated;
  • Carboxylic-containing photosensitive resin obtained by introducing an unsaturated double bond into the reaction product of a bisepoxy compound and bisphenols, and then reacting saturated or unsaturated polybasic anhydride (d);
  • Novolak-type phenol resins alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran and / or ethylene carbonate, propylene carbon Saturated or unsaturated to the reaction product obtained by reacting the unsaturated monocarboxylic acid (h) with the reaction product with cyclic carbonates, such as carbonate, butylene carbonate, and 2,3-carbonate propyl methacrylate Carboxyl group-containing photosensitive resin obtained by reacting polybasic acid anhydride (d); .
  • alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, tetrahydrofuran, tetrahydropyran and / or ethylene carbonate
  • the polyfunctional and bifunctional epoxy resins used for the synthesis are bisphenol A skeleton, bisphenol F When it becomes a compound of the linear structure which has a skeleton, a biphenyl skeleton, or a bixylenol skeleton, or its hydrogenated compound, the component which can be preferably used as an acid-modified oligomer from the viewpoint of flexibility of DFSR, etc. can be obtained.
  • the modified product of the resins of the above (7) to (10) is preferable for the bending including the urethane bond in the main chain.
  • the acid-modified oligomer may be used as the acid-modified oligomer, and specific examples of such components include ZAR-2000, ZFR-1031, ZFR-1 121 or ZFR-1 122, etc. have.
  • the above-mentioned acid-modified oligomer is the photocurable and about 15, based on the total weight of the resin composition having a thermosetting to 75 wt 0/0, or from about 20 to 50 parts by weight 0 /., Or about 25 to 45 parts by weight 0 /. It may be included in the content of.
  • the content of the acid-modified oligomer is too small, the developability of the resin composition may be lowered and the strength of the DFSR may be lowered.
  • the content of the acid-modified oligomer is too high, not only the resin composition may be excessively developed, but also uniformity may be decreased during coating.
  • the acid value of the acid-modified oligomer may be about 40 to 120 mgKOH / g, black is about 50 to 110 mgKOH / g, or 60 to 90 mgKOH / g.
  • the acid value is too low, alkali developability may be lowered.
  • the acid value is too high, it may be difficult to form a photocurable part, for example, an exposed part, by a developing solution, which makes it difficult to form a normal pattern of DFSR.
  • the resin composition which has the said photocurable property and thermosetting property contains a photopolymerizable monomer.
  • a photopolymerizable monomer may be, for example, a compound having a photocurable unsaturated functional group such as two or more polyfunctional vinyl groups, and may form a crosslink with the unsaturated functional group of the acid-modified oligomer described above to provide photocuring during exposure. Crosslinked structure can be formed.
  • the resin composition of the exposed portion facing the portion where the DFSR is to be formed can be left on the substrate without being alkali developed.
  • a liquid phase may be used at room temperature, and accordingly, the viscosity of the resin composition may be adjusted according to a coating method, It can also play a role of further improving alkali developability of the non-exposed part.
  • a (meth) acrylate-based compound having 3 or 6 photocurable unsaturated functional groups in the molecule may be used, or more specifically, pentaeri Hydroxy group-containing polyfunctional acrylate compounds such as tritriacrylate and dipentaerythritol pentaacrylate; Water-soluble polyfunctional acrylate compounds such as polyethylene glycol diacrylate or polypropylene glycol diacrylate; Polyfunctional polyester acrylate compounds of polyhydric alcohols such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, or dipentaerythr; Acrylate compounds of ethylene oxide adducts and / or propylene oxide adducts of polyfunctional alcohols such as trimethyl to propane or hydrogenated bisphenol A or polyhydric phenols such as bisphenol A and biphenol; A polyfunctional or monofunctional polyurethane acrylate compound which is an isocyanate modified product of the hydroxy group-containing polyfunctional
  • Epoxy acrylate compounds which are (meth) acrylic acid adducts of A diglycidyl ether or phenol novolac epoxy resins; Caprolactone.
  • Caprolactone modified acrylate compounds such as acrylate of a modified ditrimethyl to propane tetraacrylate, an epsilon -caprolactone modified dipentaerythr, or a caprolactone modified hydroxy pivalate neopentyl glycol ester diacrylate, and
  • One or more compounds selected from the group consisting of photosensitive (meth) acrylate-based compounds such as (meth.) Acrylate-based compounds such as the above-mentioned acrylate-based compounds may be used, and these may be used alone or in combination of two or more. Can also be used.
  • the photopolymerizable monomer a polyfunctional (meth) acrylate-based compound having two or more, or three or more black, or three to six (meth) acryloyl groups in one molecule is preferably used. And especially pentaerythritol triacrylate, trimethylolpropanetriacrylate, dipentaerythrocyte nucleoacrylate, or caprolactone modified Ditrimethylol propane tetraacrylate etc. can be used suitably.
  • Examples of commercially available photopolymerizable monomers include Kaylarad's DPEA-12 and the like.
  • the content of the aforementioned photo-polymerization monomer is from about 7 to 20 weight 0/0, the resin composition based on the total amount of about 5 to 30 parts by weight 0/0, the black is black can be about 7 to 15 weight 0 /.
  • the content of the photopolymerizable monomer is too small, the photocuring may not be divided, and when too large, the dryness of the DFSR may deteriorate and the physical properties may be degraded.
  • the photocurable and thermosetting resin composition contains a photoinitiator.
  • photoinitiators serve to initiate radical photocuring, for example, in the exposed portion of the resin composition.
  • a photoinitiator As a photoinitiator, a well-known thing can be used and it is a benzoin type
  • Irugacure registered trademark
  • an oxime ester compound is mentioned.
  • 2-aminoethyl ether 2-aminoethyl ether
  • 2-aminoethyl ether 2-aminoethyl ether
  • 2-aminoethyl ether 2-aminoethyl ether
  • 2-aminoethyl ether 2-aminoethyl ether
  • 2-aminoethyl ether 2-a specific example of an oxime ester compound
  • the content of the photoinitiator may be about 0.5 to 20 weight 0 /., Or about 1 to 10 weight 0 /. Or about 1 to 5 weight 0 /. If the content of the photoinitiator is too small, the photocuring may not occur properly, on the contrary, if the content of the photoinitiator is too large, the resolution of the resin composition may be lowered or the reliability of the DFSR may not be sufficient.
  • the photocurable and 3 ⁇ 4curable resin composition also includes a thermosetting binder having at least one member selected from thermosetting functional groups such as epoxy groups, oxetanyl groups, cyclic ether groups, and cyclic thio ether groups.
  • a thermosetting binder may form a crosslinking bond with an acid-modified oligomer and the like by thermosetting to secure heat resistance or mechanical properties of DFSR.
  • the thermosetting binder may have a softening point of about 70 to 100 ° C, thereby reducing the unevenness during lamination. Low softening points increase the tackiness of the DFSR and high flow rates can deteriorate.
  • thermosetting binder a resin having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter referred to as cyclic (thio) ether groups) in a molecule can be used, and a bifunctional epoxy resin can be used. have. Other Diisocyanate and its bifunctional block isocyanate can also be used.
  • the thermosetting binder having two or more cyclic (thio) ether groups in the molecule may be a compound having any one or two or more of three, four or five membered cyclic ether groups, or cyclic thioether groups in the molecule. have.
  • the thermosetting binder may be a polyfunctional epoxy compound having at least two or more epoxy groups in a molecule, a polyfunctional oxetane compound having at least two or more oxetanyl groups in a molecule, or an episulfide resin having two or more thioether groups in a molecule And so on.
  • the said polyfunctional epoxy compound bisphenol-A epoxy resin, hydrogenated bisphenol-A epoxy resin, brominated bisphenol-A epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, novolak-type epoxy resin, for example Phenol phenolic epoxy resin, cresol novolac epoxy resin, M-glycidyl epoxy resin, bisphenol A novolak epoxy resin, bixylenol epoxy resin, biphenol epoxy resin, chelate epoxy resin, glyox Flesh type epoxy resin, amino group-containing epoxy resin, rubber modified epoxy resin, dicyclopentadiene phenolic epoxy resin, diglycidyl phthalate resin, heterocyclic epoxy resin, tetraglycidyl xylenoylethane resin, silicone modified epoxy resin, (epsilon) -caprolactone modified epoxy resin, etc.
  • Phenol phenolic epoxy resin cresol novolac epoxy resin
  • M-glycidyl epoxy resin bisphenol A novolak epoxy resin
  • thermosetting these epoxy resins characteristics such as adhesiveness of a cured film, solder heat resistance, and electroless plating resistance are improved.
  • polyfunctional oxetane compound Bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl-3-jade Cetanylmethoxy) methyl] banzen, 1,4-bis [(3-ethyl-3-oxetanylmethoxyoxy) methyl] benzene, (3-methyl-3-oxetanyl) methylacrylate, (3-ethyl- 3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3 oxetanyl) methyl methacrylate or an oligomer or copolymer thereof
  • polyfunctional oxetanes such as oxetane alcohol, novolak resin, poly ( ⁇ -hydroxystyrene), cardo
  • YDCN-500-80P etc. of Kukdo Chemical Co., Ltd. can be used.
  • thermosetting binder may be included in an amount of 0.8 to 2.0 equivalents based on 1 equivalent of the carboxyl group of the acid-modified oligomer.
  • carboxyl groups remain in the DFSR after curing, which may lower heat resistance, alkali resistance, electrical insulation, and the like.
  • the content is too large, it is not preferable because the low molecular weight thermosetting binder remains in the dry coating film because the strength and the like of the coating film decrease.
  • the resin composition having the photocurable and thermosetting is a solvent; And at least one selected from the group consisting of a thermosetting binder catalyst (thermosetting catalyst), a filler, a pigment, and an additive to be described later.
  • thermosetting binder catalyst thermosetting catalyst
  • Thermosetting Binder Catalyst (Thermosetting Catalyst)
  • thermosetting binder catalyst serves to promote thermosetting of the thermosetting binder.
  • thermosetting binder catalyst for example, imidazole, 2-methylimidazole- 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole Imidazole derivatives such as 2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) - ⁇ , ⁇ -dimethylbenzylamine, 4-methoxy- ⁇ , ⁇ -dimethylbenzylamine, 4-methyl- ⁇ , ⁇ -dimethylbenzylamine compound; Hydrazine compounds such as adipic dihydrazide and sebacic acid dihydrazide; Phosphorus compounds, such as a triphenylphosphine, etc.
  • imidazole 2-methylimidazole- 2-ethylimidazole, 2-e
  • thermosetting catalyst of an epoxy resin or an oxetane compound or it promotes reaction of an epoxy group and / or an oxetanyl group, and a carboxyl group, and can also be used individually or in mixture of 2 or more types. .
  • guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-tree Azine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl -S-triazine ⁇ isocyanuric acid S-triazine derivatives, such as an adduct, can also be used,
  • the compound which also functions as these adhesive imparting agents can be used together with the said thermosetting binder catalyst.
  • the content of the thermosetting binder catalyst may be about 0.3 to 15 weight 0 / .about the total weight of the resin composition described above, in terms of suitable thermosetting.
  • the filler serves to improve heat stability, thermal dimensional stability and resin adhesion. In addition, it also serves as a constitution pigment by reinforcing the color.
  • a filler can be inorganic or organic fillers, such as barium sulfate, barium titanate, amorphous silica, crystalline silica, molten silica, spherical silica, talc,. Clay, magnesium carbonate, calcium carbonate, aluminum oxide (alumina), aluminum hydroxide, mica and the like can be used.
  • the content of a filler is about 5 to 50 weight 0 /. With respect to the total weight of the resin composition mentioned above. In the case of using more than 50 weight 0 /., The viscosity of the composition becomes high and the coating property is lowered or the degree of curing is poor, which is not preferable.
  • Pigments exhibit visibility and hiding power to hide defects such as scratches on circuit lines.
  • a red, blue, green, yellow, or dark pigment may be used.
  • Phthalocyanine blue, pigment blue 15: 1, pigment blue 15: 2, pigment blue 15: 3, pigment blue 15: 4, pigment blue 15: 6, pigment as a blue pigment Blue 60, etc. can be used.
  • Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28 and the like can be used as the green pigment.
  • the yellow pigments include anthraquinones, isoindolinones, condensed azos, and benzimidazolones.
  • the content of the pigment is preferably used at about 0.5 to 3 weight 0 /. Relative to the total weight of the resin composition. When using less than 0.5 weight 0 /. When used in visibility, and the hiding power drops, exceeding 3 parts by weight 0/0, will drop in heat resistance.
  • the additive may be added to remove bubbles of the resin composition, or to remove the popping and craters on the surface of the film, to impart flame retardancy, to control viscosity, and to provide a catalyst.
  • the silica powder such as an organic bentonite, montmorillonite, thickeners conventionally known; Antifoaming agents and / or leveling agents such as silicone-based, fluorine-based and polymer-based; Silane coupling agents such as imidazole series, thiazole series, and triazole series; Known and common additives such as phosphorus flame retardants and flame retardants such as antimony flame retardants can be blended.
  • the leveling agent serves to remove the popping or craters of the surface when the film is coated, for example, BYK-380N, BYK-307, BYK-307, BYK-378, BYK-350 of BYK-Chemie GmbH.
  • the content of the additive is about 0.01 to about the total weight of the resin composition
  • Is increased from 10 0/0 is preferred.
  • Ketones such as methyl ethyl ketone and cyclonucleanone
  • Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene
  • Ethylene glycol monoethyl ether ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, Diethylene glycol monoethyl ether, diethylene glycol monomethyl ether diethylene glycol monobutyl ether, propylene glycol monomethyl ether propylene glycol monoethyl ether, dipropylene glycol diethyl ether triethylene glycol monoethyl ether glycol ether (cellosolve ), Ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether: teracetate,
  • Acetate esters such as dipropylene glycol monomethyl ether acetate
  • Alcohols such as ethanol, propanol, ethylene glycol, propylene glycol and carbyl
  • Octane decane aliphatic hydrocarbons
  • Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha
  • Amides such as dimethylacetamide and dimethylformamide (DMF).
  • the solvent content is about 10 to about the total weight of the resin composition described above.
  • 50 weight can be 0 /. If it is less than 10% by weight, the viscosity is high, the coating property is inferior, and if it exceeds 50% by weight 0 /.
  • DFSR having fine irregularities on the surface is formed by using the above-described photocurable and thermosetting resin composition.
  • these DFSR and the formation process will be described for each step.
  • 1A to 1E are process flowcharts schematically illustrating a process of forming DFSR having fine concavities and convexities in a manufacturing method according to an embodiment of the present invention.
  • the resin composition 110 having the photocurable and thermosetting properties including the above-described components has an average roughness (Ra) of about 50 nm to 5, and black on the surface thereof. Is formed on the transparent carrier film 100 on which fine unevennesses of about 200 nm to 2 / ⁇ , or about 250 nm to 1, or about 300 nm to 500 nm are formed. Transparent formed with these fine irregularities As the resin composition 110 is formed on the carrier film 100, fine irregularities on the transparent carry film 100 are reflected on the resin composition 110 and the DFSR formed therefrom to finally obtain DFSR having fine irregularities. It can manufacture.
  • Ra average roughness
  • the transparent carrier film 100 needs to exhibit excellent transparency and light transmittance and low haze characteristics so that the resin composition 110 may be irradiated with ultraviolet rays through the exposure process in a subsequent process.
  • the transparent carrier film may exhibit a light transmittance of about 90% or more, or about 92 to 100% and a haze of about 5% or less, or about 1 to 4%.
  • the transparent carrier film 100 does not have to be limited to show the above light transmittance and haze, and in some cases, it is not relatively high of about 65% or more, for example, about 65 to 80%. It is also possible to use a transparent carrier film 100 such as matt PET exhibiting light transmittance.
  • the transparent carrier film 100 fine irregularities are formed on the surface.
  • an inorganic filler may be injected into a predetermined transparent plastic film, and the transparent plastic film having fine unevenness formed through the injection of such an inorganic filler may be laminated with another flat transparent plastic film to make the transparent
  • the appropriate thickness of the carrier film 100 can be adjusted.
  • a transparent plastic film in which fine unevenness is directly formed through the above-described method may be used, or a commercially available transparent plastic film having fine unevenness may be obtained and used commercially.
  • the average roughness (Ra) is about 50 nm to 5 H1, or about 200 nm to zm, or about 250 nm to ⁇ m, or so as to enable good formation of DFSR having fine irregularities of appropriate size. Fine unevenness may be formed that is about 300 nm to 500 nm. If the average roughness Ra of the fine unevenness is too small, it may be impossible to form fine unevenness having an appropriate size on the DFSR surface. On the contrary, when the average roughness (Ra) of the fine unevenness is too large, light scattering may occur excessively in the exposure process due to such unevenness on the transparent carrier film 100. In addition, good DFSR may not be formed. of It may be disadvantageous to secure the haze, and there may be a problem in that a gap may be formed during adhesion with subsequent materials in the manufacturing process of the semiconductor device.
  • the transparent carrier film 100 may be easily removed from the photocured resin composition 110 by appropriately performing the subsequent exposure process, and may be formed so that the fine irregularities of the size described above may be properly formed and maintained on the surface.
  • 5 to 30 // m, black may have a thickness of about 12 to 25.
  • a plastic film which satisfies physical properties such as transparency, fine concavo-convex size and thickness described above can be used, and for example, a polyester film or a polyolefin film can be used. More specific examples thereof include polyester films such as PET films including matt polyethylene terephthalate (PET) films, and polyolefin films such as polypropylene films.
  • PET polyethylene terephthalate
  • polyolefin films such as polypropylene films.
  • the resin composition 110 as a photosensitive coating material, a comma coater, a blade coater, Lip coaters, rod coaters, squeeze coaters, reverse coaters, transfers can be applied onto the transparent carrier film 100 with a coater, a gravure coater, a spray coater, or the like.
  • coating on the transparent carrier film 100 the resin composition 110 on this transparent carrier film 100 can be dried. For this drying, the transparent carrier film 100 on which the resin composition 110 is formed is placed in an oven at a temperature of about 50 to 130 ° C., about 60 to 120 ° C.
  • the resin composition 110 on the transparent carrier film 100 may be in a semi-dry state having a viscosity raised to some extent.
  • the elevated viscosity of this semi-dried resin composition 110 can be expressed by its gelation time.
  • the semi-dry resin composition 110 may have a gelation time of about 2 to 5 minutes, or about 2 minutes 30 seconds to 4 minutes 30 seconds under the conditions of 0.4g and 16C C.
  • the gelation time is a gel time measuring device, for example, a gel time measuring device such as the model name DH-15 of Daeheung Science.
  • the measuring temperature can be measured by setting a measuring temperature of 160 ° C in such a measuring device, and taking about 0.5 g of the resin composition 110 into the measuring device and slowly stirring with an insulator such as a wooden rod to visually observe the gelling time. It can be measured. In this way, the measured value of the gelation time can be determined by the average value derived by measuring the gelation time three times repeatedly.
  • a release film or the like described later is attached to the resin composition to proceed with a subsequent DFSR forming process (forming process on the substrate of the resin composition, exposure and developing process, etc.). It can be carried out in order to remove the release film, etc. immediately before the DFSR forming process can proceed to the subsequent process. If the viscosity of the resin composition after drying is too low, it may not be suitable for the transfer for the subsequent process, and conversely, if the viscosity of the resin composition after the drying is too high, it may be unsuitable for the subsequent process. Can be.
  • a release film (Release Rim) ol may be formed on the resin composition (1 10).
  • a release film is formed between the process of forming the said resin composition (10) on the transparent carrier substrate 100, and the following DFSR formation process (formation process on the board
  • a release film a polyethylene (PE) film, a polytetrafluoroethylene film, a polypropylene film, a polyethylene terephthalate (PET) film, or a surface treated paper may be used, and when the release film is peeled off, the resin composition ( It is preferable that the adhesive force of the said resin composition (10) and a release film is lower than the adhesive force of the 110 and the transparent carrier film 100.
  • PE polyethylene
  • PET polyethylene terephthalate
  • the resin composition 110 is a transparent carrier.
  • the film laminate after formation on the substrate 100 and after drying has progressed may be provided as an intermediary for the production of DFSR. These film laminates have an average roughness (Ra) of about 50 nm on the surface.
  • the film laminate may further include a release film formed on the resin composition layer as described above.
  • the resin composition 110 may be laminated on a package substrate of a semiconductor device to form a laminated structure in which the substrate 120, the resin composition 110, and the transparent carrier film 100 are sequentially formed.
  • the release film described above may be peeled from the resin composition 110 immediately before the forming step of such a laminated structure.
  • the transparent carrier film 100 having the resin composition 1 10 formed thereon is a vacuum laminator, a hot laminator or a vacuum press so that the resin composition 1 10 is formed on the substrate 120. Or the like may be bonded onto the substrate 120.
  • the transparent resin substrate 100 may be exposed to the resin composition 110 through the transparent carrier substrate 100, and the transparent carrier film 100 may be peeled off.
  • the exposure process may be performed by irradiating light such as ultraviolet rays having a constant wavelength band, and may be selectively exposed through a photomask, or may be directly exposed to a pattern by a laser direct exposure machine. Since the exposure process proceeds through the transparent carrier film 1 10 having the fine unevenness formed on the surface, light scattering due to the fine unevenness occurs during the exposure, so that selective exposure may not be easily performed. In consideration of this, the exposure process may be performed with an increased exposure amount than in the exposure process for forming a known DFSR.
  • Such exposure dose is a thickness to be exposed, for example, the transparent
  • the exposure process may be performed by a method of irradiating ultraviolet rays with the exposure amount thus determined.
  • the exposure process may be appropriately performed while reducing the influence of light scattering, whereby DFSR having fine unevenness may be formed well.
  • the exposure process described above is carried out, for example, in the exposed portion, the unsaturated functional groups contained in the acid-modified oligomer in the resin composition (10) and the unsaturated functional groups contained in the photopolymerizable monomer cause photocuring and crosslink with each other.
  • the resin composition 110 of such an exposed part may be in a state that cannot be removed by a subsequent alkali development process, and photocuring proceeds while reflecting the fine unevenness of the surface of the transparent carrier substrate 100, thereby causing crosslinking of the exposed part.
  • the resin composition 110 may be formed in a shape having fine concavo-convex on the surface in contact with the transparent carrier substrate 100.
  • the carboxyl group of an acid-modified oligomer is maintained as it is, and it can be in the state which can develop alkali.
  • the transparent carrier film 100 After advancing the said exposure process, the transparent carrier film 100 can be peeled off.
  • the transparent carrier film 100 When the transparent carrier film 100 is peeled off prior to exposure, the peeling may not be performed well due to the adhesive strength with the resin composition 1 10, and the subsequent process may be difficult. In consideration of this, the transparent carrier film 100 may be peeled off after exposure.
  • the resin composition 110 of a non-exposure part is developed using alkaline solution etc.
  • an alkaline solution for carrying out such a developing step an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, or amines can be used.
  • an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, or amines can be used.
  • the acid-modified oligomer, the photopolymerizable monomer, etc. of a non-exposed part can melt
  • the resin composition 1 10 can be left only in the desired portion on the substrate facing the exposed portion to form the DFSR, and as described above, the DFSR (resin composition; 1 10) is because the fine irregularities of the surface of the transparent carrier film 100 may be reflected to have a fine irregularities on the surface, it is easier to manufacture a DFSR having fine irregularities without changing the composition or the change of the process, such as a plasma treatment process You can do it.
  • DFSR can be finally formed by heat curing the resin composition 110 on the substrate 120 (Post Cure).
  • the heat curing temperature is suitably about 10 C C or more.
  • the thermosetting functional group of the thermosetting binder included in the resin composition (1 10) and the carboxyl group of the acid-modified oligomer may be crosslinked to form a crosslinked structure.
  • fine unevennesses having an average roughness (Ra) of about 50 nm to 5 // m, or about 200 nm to 2, or about 250 nm to 1 Pa, or about 300 nm to 500 nm are formed on the surface.
  • the DFSR can be finally formed.
  • a DFSR and a printed circuit board including the same for example, a package substrate of a semiconductor device may be provided, and the DFSR contacts a subsequent process material and the like as predetermined fine unevenness is formed on a surface thereof.
  • the surface area can be increased to show good adhesion.
  • the DFSR is the acid-modified oligomer described above as the photocuring and thermal curing; Photopolymerizable monomers; And a cured product of a thermosetting binder having a thermosetting functional group.
  • the carboxyl group of the acid-modified oligomer may be crosslinked with a thermosetting functional group of a thermosetting semi-unggi group by thermosetting, and the photocurable unsaturated functional group of the acid-modifying oligomer
  • the crosslinking may be carried out by crosslinking with the unsaturated functional groups included in the photopolymerizable monomer.
  • fine ruggedness may be formed on the surface of the DFSR.
  • DFSR having fine irregularities formed on the surface can be formed in an easier and simplified manner without adding or changing a process such as a separate plasma treatment or changing a composition, a subsequent process when applied to a semiconductor package substrate or the like. While it is possible to provide DFSR showing excellent adhesion to materials, it is possible to change or decrease the physical properties of DFSR due to process or composition change. It becomes possible to provide DFSR which suppresses and expresses and maintains excellent physical properties.
  • the DFSR may further include a small amount of photoinitiator remaining in the cured product after participating in photocuring.
  • DFSR having fine unevennesses on the surface can be formed by a simpler method using only a transparent carrier film having surface fine unevennesses without adding or changing a process such as a plasma treatment process or changing the composition.
  • 1A to 1E are process flowcharts schematically illustrating a process of forming DFSR having fine unevenness by a manufacturing method according to an embodiment of the present invention.
  • 2 and 3 show surface conditions of the DFSR formed in Examples 1 and 2.
  • 4A and 4B are 2D images and 3D images measured with an OP (Optical profiler) to calculate the surface roughness of the DFSR formed in Comparative Example 1.
  • 5A and 5B are 2D images and 3D images measured with an OP (Optical profiler) to calculate the surface roughness of the DFSR formed in Example 1.
  • Darocur TPO (Ciba Specialty Chemicals Inc.), the YDCN-500-80P (Kukdo Chemical Co.) in 3 parts by weight 0/0, a thermoset binder a photoinitiator 16 weight 0 /.
  • 2-phenyl imidazole is a 1 weight 0 / 15 weight 0 / ⁇ of ⁇ -30 (Sakai Chemical Co., Ltd.) as a filler, 0.5 wt% of ⁇ ⁇ ⁇ -333 from ⁇ as an additive, and 13 wt% of this IF as a solvent to mix and stir each component.
  • the filler was dispersed in a mill mill to prepare a resin composition having photocurability and thermosetting.
  • the resin composition prepared above was applied to PET used as a transparent carrier film using a comma coater. At this time, SKC's SD-15 product was used as the transparent carrier film, and fine irregularities having an average roughness of about 344.67 nm (Ra) and about 636 kW (Rz) were formed on the transparent carrier film. 20 was.
  • the photosensitive film layer was vacuum laminated with a vacuum laminator (MV LP-500 manufactured by Meisei Seisakusho Co., Ltd.) on a substrate on which a circuit was formed, and then 400 mJ / After exposing to cm 2 , the PET film was removed. Subsequently, the resultant was immersed in a stirring solution of 31 ° C. Na 2 CO 3 1% for 60 seconds, followed by development and heat curing at 15 CTC for 1 hour to complete a printed circuit board including dry film solder resist (DFSR). It was.
  • a stirring solution 31 ° C. Na 2 CO 3 1% for 60 seconds
  • the substrate on which the circuit is formed has a thickness of 5 cm and a length of 5 cm for the LG-C-500GA copper-clad laminate LG-T-500GA having a thickness of 0.1 mm and a copper foil thickness of 12. It cut into the board
  • An acid-modified oligomer is a ZFR-1122 of Nippon Kayaku as 41.5 weight 0/0, a photopolymerizable monomer functional epoxy acrylate as (DPEA-12 of Nippon Kayaku), 10 parts by weight 0/0, the photoinitiator Darocur TPO (Ciba Specialty Chemicals Inc.) for the ⁇ -30 (Sakai Chemical Co., Ltd.) as a third increment 0/0, YDCN-500-80P (Kukdo Chemical Co.) 16 wt% of a thermosetting binder, a thermal curing catalyst 2-phenyl-1% by weight of the imidazole, the filler 15 % by weight, and as an additive using DMF 13 parts by weight 0/0 to ⁇ -333's ⁇ as 0.5 0/0, a solvent for a photo-curable and heat-curable by combining the components and dispersing the filler in three reulmil equipment after stirring
  • the resin composition prepared above was applied to PET used as a transparent carrier film using a comma coater. At this time, a product of Toray Co., Ltd. was used as the transparent carrier film. Fine unevennesses having an average roughness of about 405 nm (Ra) and about 11.67 (Rz) were formed, and the thickness was about 23 / m . It was.
  • the photosensitive film layer was vacuum-laminated on the board
  • LP-500 was vacuum laminated, and then exposed to 400 mJ / cm 2 under UV of 365 nm wavelength band, and then the PET film was removed.
  • the resultant was immersed in an alkali solution of 1% Na 2 CO 3 at 31 ° C. for 60 seconds, and then developed and heat-cured at 150 ° C. for 1 hour, thereby including a printed circuit board including dry film solder resist (DFSR).
  • DFSR dry film solder resist
  • the substrate on which the circuit is formed is cut LG substrate copper-clad LG-T-500GA of 0.1mm thickness, copper foil thickness 12 / m into a substrate of 5cm width and 5cm length, and fine roughness on the surface of the copper foil by chemical etching What was formed was used. .
  • Example 3
  • thermosetting binder 2-phenylimidazole as 1 weight 0 / O as a thermosetting catalyst, ⁇ -30 (Saka Chemical) as a filler 15% by weight, the photo-curable and heat-curable by dispersing the filler in three roll mill equipment after blending the components and stirring by using a ⁇ -333's ⁇ 0.5 increase% and 13 in DMF as a solvent by weight 0/0 as an additive
  • the resin composition which has is manufactured.
  • the resin composition prepared above was applied to PET used as a transparent carrier film using a comma coater. At this time, a product of Toray Co., Ltd. was used as the transparent carrier film. Fine irregularities having an average roughness of about 500 nm (Ra) and about 26.71 (Rz) were formed on the transparent carrier film, and the thickness was about 19.
  • the photosensitive film layer was vacuum laminated with a vacuum laminator (MV LP-500 manufactured by Meisei Seisakusho Co., Ltd.) on a substrate on which a circuit was formed, and then 400 mJ / After exposing to cm 2 , the PET film was removed. Subsequently, the resultant was immersed in a stirring 31 ° C. Na 2 CO 3 1% alkaline solution for 60 seconds, and then developed and heat cured at 150 ° C. for 1 hour, thereby including a printed circuit board including dry film solder resist (DFSR). Was completed.
  • a vacuum laminator MV LP-500 manufactured by Meisei Seisakusho Co., Ltd.
  • the substrate on which the circuit was formed was cut into a copper-clad laminate LG-T-500GA of LG Chemical having a thickness of 0.1 mm and a copper thickness of 12 into a substrate having a width of 5 cm and a length of 5 cm.
  • a copper-clad laminate LG-T-500GA of LG Chemical having a thickness of 0.1 mm and a copper thickness of 12 into a substrate having a width of 5 cm and a length of 5 cm. was used.
  • the filler 30 to 15 parts by weight 0 / (Sakai Chemical Co., Ltd.), and then blending the components using a 13 increment 0 /. a DMF a ⁇ -333's ⁇ as 0.5 0/0, the solvent, as an additive, which was stirred for 3 roll mill equipment
  • the filler was dispersed to prepare a resin composition having photocurability and thermosetting property.
  • the photosensitive film layer was vacuum laminated with a vacuum laminator (MV LP-500 manufactured by Meisei Seisakusho Co., Ltd.) on a substrate on which a circuit was formed, and then 400 mJ / After exposing to cm 2 , the PET film was removed. Subsequently, the resultant was immersed in an agitated alkaline solution of Na 2 CO 3 1% at 31 ° C. for 60 seconds, followed by development and heat curing at 15 C C for 1 hour to form a printed circuit board including a dry film solder resist (DFSR). Completed.
  • a vacuum laminator MV LP-500 manufactured by Meisei Seisakusho Co., Ltd.
  • the substrate on which the circuit is formed is cut to LG Chem's copper-clad laminate LG-T-500GA having a thickness of 0.1 mm and a copper foil thickness of 12 m into a substrate having a width of 5 cm and a length of 5 cm to form fine roughness on the surface of the copper foil by chemical etching.
  • LG Chem's copper-clad laminate LG-T-500GA having a thickness of 0.1 mm and a copper foil thickness of 12 m into a substrate having a width of 5 cm and a length of 5 cm to form fine roughness on the surface of the copper foil by chemical etching.
  • a negatively drawn quartz photomask was placed on the laminated DFSR and exposed to UV (i band) of 400 mJ / cm 2 , and then the PET film used as a carrier film was removed, and Na 2 at 30 ° C. After developing for 60 seconds in an alkali solution of CO 3 1%, washed with water and dried.
  • Example 1 and Comparative Example 1 The surface of the dried sample was observed using FE-SEM (Hitachi S-4800); and in Example 1 and Comparative Example 1, using OP (Optical profiler) to accurately measure the difference in average roughness It measured by comparing the value of average roughness value Ra.
  • FE-SEM photographs of the surface states of Examples 1 and 2 are as shown in Figs. 2 and 3, and the images measured using the OP for Example 1 and Comparative Example 1 are shown in Fig. 4A (Comparative Example 1 2D-image), 4B (3D-image of Comparative Example 1), 5A (2D-image of Example 1) and 5B (3D-image of Example 1).
  • the Ra values measured in Examples 1 and 2 were as summarized in Tables 1 and 2 below.
  • a negatively drawn quartz photomask was placed on the laminated DFSR, exposed to UV (i band) of 400 mJ / cirf, and then the PET film used as a carrier film was removed, and Na 2 CO at 30 ° C. 3 1% alkali. The solution was developed for 60 seconds, washed with water and dried.
  • the protective film for printed circuit board was laminated on CCL, and finished through photocuring, thermal curing and back curing, and then cut to 150mm * 130mm.
  • a temperature of 288 ° C was set in the bath (electrically heated, temperature-controlled and at least 2.25 kg of lead for testing), and the test specimen was placed with the film on top of the bath. The test specimens were inspected for visible peeling or deformation of the film.
  • the gelation time for each resin composition was measured by the following method.
  • a gel time meter of DH-15 was used, and the measuring temperature was set at 16 C C. About 0.5 g of the resin composition was collected and placed in the meter, and the wooden rod was stired slowly about twice per second using a wooden rod. Stirred. The time of gelation by visual observation with this stirring was measured. In this way, the measured value of the gelation time was determined from the average value derived by measuring the gelation time three times repeatedly. Of such gelation time The measurement results are summarized in Table 4 below.
  • composition of Examples 1 to 3 may have a suitable viscosity defined by the gelation time after the drying process, to proceed to the subsequent process to enable the appropriate preparation of DFSR having fine irregularities It was confirmed.

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Abstract

La présente invention concerne un procédé de préparation d'une épargne de soudage et film sec permettant de former, selon un procédé plus simplifié, une épargne de soudage et un film sec présentant des micro-parties saillantes superficielles; l'invention concernant également un stratifié pelliculaire utilisé dans ce procédé. Le procédé de préparation d'une épargne de soudage et d'un film sec comprend les étapes consistant à : former une composition de résine photodurcissable et thermodurcissable prédéterminée sur un film de support transparent présentant des micro-parties saillantes superficielles ayant une rugosité moyenne (Ra) de 200 nm à 2 µm ; former une structure en couches dans laquelle un substrat, la composition de résine et le film de support transparent sont formés successivement par superposition de couches de la composition de résine sur le substrat ; exposer la composition de résine et éliminer le film de support transparent ; et effectuer le développement alcalin de la composition de résine d'une portion non exposée et procéder à son thermodurcissement.
PCT/KR2014/008791 2013-09-24 2014-09-22 Procédé de préparation d'épargne de soudage et film sec, et stratifié pelliculaire utilisé dans ce procédé WO2015046842A1 (fr)

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US14/763,414 US9788434B2 (en) 2013-09-24 2014-09-22 Preparation method for dry film solder resist and film laminate used therein
CN201480013033.8A CN105190442B (zh) 2013-09-24 2014-09-22 阻焊干膜的制备方法以及其中使用的层压膜
JP2015546407A JP6047666B2 (ja) 2013-09-24 2014-09-22 ドライフィルムソルダーレジストの製造方法と、これに用いられるフィルム積層体

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KR1020130113179A KR101734425B1 (ko) 2013-09-24 2013-09-24 드라이 필름 솔더 레지스트의 제조 방법과, 이에 사용되는 필름 적층체
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CN105190442A (zh) 2015-12-23
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TWI565589B (zh) 2017-01-11
US20150366070A1 (en) 2015-12-17
JP6047666B2 (ja) 2016-12-21
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US9788434B2 (en) 2017-10-10

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